DE2614234C2 - Treatment liquid for the corrosion protection of metal surfaces and concentrate for their production - Google Patents
Treatment liquid for the corrosion protection of metal surfaces and concentrate for their productionInfo
- Publication number
- DE2614234C2 DE2614234C2 DE2614234A DE2614234A DE2614234C2 DE 2614234 C2 DE2614234 C2 DE 2614234C2 DE 2614234 A DE2614234 A DE 2614234A DE 2614234 A DE2614234 A DE 2614234A DE 2614234 C2 DE2614234 C2 DE 2614234C2
- Authority
- DE
- Germany
- Prior art keywords
- treatment liquid
- acid
- reaction product
- liquid according
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000011282 treatment Methods 0.000 title claims description 32
- 239000007788 liquid Substances 0.000 title claims description 25
- 238000005260 corrosion Methods 0.000 title claims description 18
- 230000007797 corrosion Effects 0.000 title claims description 16
- 239000012141 concentrate Substances 0.000 title claims description 13
- 229910052751 metal Inorganic materials 0.000 title claims description 12
- 239000002184 metal Substances 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 24
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 13
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000174 gluconic acid Substances 0.000 claims description 12
- 235000012208 gluconic acid Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 22
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 11
- 235000008504 concentrate Nutrition 0.000 description 11
- 229960002446 octanoic acid Drugs 0.000 description 11
- -1 alkanolamines Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000012084 conversion product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000008233 hard water Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001214257 Mene Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000005068 cooling lubricant Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
Die Erfindung betrifft eine wäßrige Behandlungsflüssigkeit zum Korrosionsschutz von Metalloberflächen mit einem Gehalt an einem Umsetzungsprodukt von mindestens zwei unterschiedlichen Carbonsäuren, wovon eine Carbonsäure eine aliphatische Carbonsäure ist, mit Alkanolamin im Überschuß.The invention relates to an aqueous treatment liquid for protecting metal surfaces from corrosion with a content of a reaction product of at least two different carboxylic acids, of which a carboxylic acid is an aliphatic carboxylic acid, with an excess of alkanolamine.
Zur Vermeidung unerwünschter Korrosionserscheinungen ist die Behandlung mit wäßrigen Lösungen, die
korrosionsinhibierende Zusätze enthalten, üblich. Die Anwendung solcher mehr oder weniger stark alkalischer
Lösungen erfolgt insbesondere zum vorübergehenden Korrosionsschutz während des Fertigungsablaufs
metallischer Werkstücke, bei oder nach Reinigungsbehandlungen, bei der spanabhebenden
Bearbeitung oder bei Zwischenlagerungen vor weiteren Behandlungsstufen. Bekannte korrosionsinhibierende
Zusätze sind beispielsweise Alkalinitrite, Alkalichromate oder organische Verbindungen, wie Alkanolamine,
besonders Triethanolamin, oder Alkali- oder Alkanolaminseifen
von Fettsäuren mittlerer Kettenlänge. Nitrite und Chromate weisen den Nachteil auf, daß die
Lösungen vor der Ableitung in das Abwasser durch besondere Maßnahmen aufbereitet werden müssen. Der
mit Alkanolaminen oder den Fettsäuresalzen erzielbare Korrosionsschutz ist vielfach nicht ausreichend, so daß
den Lösungen zusätzlich Nitrit zugegeben wird, was jedoch wieder zu dem genannten anwendungstechnischen
Nachteil führt
Weiterhin ist eine Antirostadditiv-Zubereitung bekannt
(DE-OS 24 26 114), die zumindest ein Salz zumindest einer aliphatischen Carbonsäure mit 6 bis
20 Kohlenstoffatomen pro Molekühl mit zumindest einem Alkanolamin,
zumindest ein Salz zumindest einer aromatischen Carbonsäure mit bis zu 20 Kohlenstoffatomen pro
Molekül mit zumindest einem Alkanolamin,
bei einem bestimmten Gewichtsverhältnis der genannten Carbonsäuren zueinander sowie freies Alkanolamin
enthält Die Verwendung dieser Zubereitung ist jedoch mit dem Nachteil verbunden, daß es auf der
Metalloberfläche zu kristallinen Auftrocknungen kommen kann, insbesondere wenn zur Herstellung einer
wäßrigen Emulsion hartes Wasser verwendet wird.
Aufgabe der Erfindung ist, eine Behandlungsflüssigkeit zum Korrosionsschutz von Metallen vorzuschalgen,
die sich durch eine hohe Korrosionsschutzwirkung, vielseitige Anwendbarkeit und abwassertechnische
Unschädlichkeit auszeichnet.Treatment with aqueous solutions containing corrosion-inhibiting additives is customary in order to avoid undesirable corrosion phenomena. The use of such more or less strongly alkaline solutions takes place in particular for temporary corrosion protection during the production process of metallic workpieces, during or after cleaning treatments, during machining or during intermediate storage before further treatment stages. Known corrosion-inhibiting additives are, for example, alkali nitrites, alkali chromates or organic compounds such as alkanolamines, especially triethanolamine, or alkali or alkanolamine soaps of fatty acids of medium chain length. Nitrites and chromates have the disadvantage that the solutions have to be treated by special measures before they are discharged into the waste water. The corrosion protection that can be achieved with alkanolamines or the fatty acid salts is often inadequate, so that nitrite is additionally added to the solutions, which, however, again leads to the aforementioned disadvantage in terms of performance
Furthermore, an anti-rust additive preparation is known (DE-OS 24 26 114) which contains at least one salt of at least one aliphatic carboxylic acid with 6 to 20 carbon atoms per molecule with at least one alkanolamine,
at least one salt of at least one aromatic carboxylic acid with up to 20 carbon atoms per molecule with at least one alkanolamine,
at a certain weight ratio of said carboxylic acids to one another and also contains free alkanolamine. The use of this preparation has the disadvantage that crystalline drying can occur on the metal surface, especially when hard water is used to produce an aqueous emulsion.
The object of the invention is to propose a treatment liquid for the corrosion protection of metals, which is characterized by a high corrosion protection effect, versatile applicability and wastewater harmlessness.
Diese Aufgabe wird gelöst, indem die eingangs genannte wäßrige Behandlungsflüssigkeit gekennzeichnet ist durch ein Umsetzungsprodukt eines Gemisches ausThis object is achieved by characterizing the aqueous treatment liquid mentioned at the outset is characterized by a reaction product of a mixture
a) einer oder mehreren aliphatischen Carbonsäuren mit 6 bis 10 C-Atomen unda) one or more aliphatic carboxylic acids with 6 to 10 carbon atoms and
b) Gluconsäure und/oder Weinsäure mitb) gluconic acid and / or tartaric acid with
c) einem oder mehreren Alkanolaminen, wobei auf 1 Mol der Säurekombination mindestens 1,3 Mol
Alkanolamin vorliegt.
Es wurde überraschenderweise festgestellt, daß durch die Verwendung des genannten Säuregemisches und
den angegebenen Mindestüberschuß an Alkanolamin eine erheblich verbesserte Korrosionsschutzwirkung
erzielt wird.c) one or more alkanolamines, at least 1.3 mol of alkanolamine being present for 1 mol of the acid combination.
It was surprisingly found that the use of the acid mixture mentioned and the specified minimum excess of alkanolamine achieve a considerably improved corrosion protection effect.
Der Überschuß an Alkanolamin ist an sich nicht begrenzt, doch werden bei einem Mol-Verhältnis über 1 :3 in den meisten Fällen keine weiteren Verbesserungen erzieltThe excess of alkanolamine is not limited per se, but with a molar ratio over 1: 3 achieved no further improvements in most cases
Zweckmäßigerweise enthält die Behandlungsflüssigkeit ein Umsetzungsprodukt, in dem das Gewichtsverhältnis zwischen a) und b) 1 :0,5 bis 1 :7, vorzugsweise 1 :1 bis 1 :3, beträgt.The treatment liquid expediently contains a reaction product in which the weight ratio between a) and b) 1: 0.5 to 1: 7, preferably 1: 1 to 1: 3.
Besonders gute Ergebnisse werden erhalten, wenn eine aliphatische Carbonsäure mit 8 C-Atomen eingesetzt wird. Als Alkanolamin werden vorzugsweise Diäthanolamin und/oder Monoäthanolamin verwendet. Triethanolamin führt zu einer nicht so hohen Verstärkung der Korrosionsschutzwirkung.Particularly good results are obtained when an aliphatic carboxylic acid with 8 carbon atoms is used will. Diethanolamine and / or monoethanolamine are preferably used as the alkanolamine. Triethanolamine does not increase the anti-corrosion effect so much.
Für die Anwendung der erfindungsgemäßen Behandlungsflüssigkeit ist ein pH-Wert der Lösung von 7,5 bis 10 erwünscht. Dieser wird im allgemeinen bereits durch den Zusatz des Umsetzungsproduktes erzielt. Vorzugsweise sollte der pH-Wert der Behandlungsflüssigkeit im Bereich von 8,0 bis 9,5 liegen. Die Lösung enthält dasFor the application of the treatment liquid according to the invention, the pH of the solution is from 7.5 to 10 desired. This is generally achieved by adding the reaction product. Preferably the pH of the treatment liquid should be in the range from 8.0 to 9.5. The solution contains that
Umsetzungsprodukt zweckmäßig in einer Konzentration von 0,5 bis 5 Gew.-%.Reaction product expediently in a concentration of 0.5 to 5% by weight.
Wenn nur schwach alkalische Behandlungsflüssigkeiten gewünscht sind, um z. B. den Angriff auf bestimmte Metalle, wie Aluminium, niedrig zu halten oder die Lösungen nach Gebrauch ohne Neutralisation in das Abwasser ablassen zu können, ist eine Senkung des sich durch Lösung des Umsetzungsproduktes in Wasser ergebenden pH-Wertes in einem schmalen Bereich von etwa 0,5 Einheiten durch Zusatz von anorganischen oder organischen Säuren möglich, ohne daß eine Verschlechterung der Wirksamkeit der erfindungsgemäß eingesetzten Behandlungsflüssigkeiten eintritt Geeignete Säuren sind beispielsweise Schwefelsäure, Amidosulfosäure, Phosphorsäure, Borsäure, Adipinsäure, Maleinsäure, Phthalsäure oder Benzoesäure.If only weakly alkaline treatment liquids are desired, e.g. B. to keep the attack on certain metals, such as aluminum, low or to be able to drain the solutions into the wastewater after use without neutralization, is a reduction in the pH value resulting from the dissolution of the reaction product in water in a narrow range of about 0 , 5 units possible by adding inorganic or organic acids without impairing the effectiveness of the treatment liquids used according to the invention. Suitable acids are, for example, sulfuric acid, amidosulfonic acid, phosphoric acid, boric acid, adipic acid, maleic acid, phthalic acid or benzoic acid.
Die erfindungsgemäßen Behandlungsflüssigkeiten weisen nicht nur den Vorteil einer hohen KorroEionsschutzwirkung auf, wie sich auch aus den nachstehenden Beispielen ergibt, sondern zeigen auch eine nur geringe Schaumneigung, was sich besonders günstig auswirkt, wenn eine Anwendung im Spritzverfahren erfolgen soll. Darüber hinaus ist eine gute Beständigkeit auch in hartem Wasser gegeben. Auf den behandelten Metalloberflächen ergeben sich keine kristallinen Auftrocknungen. Die Behandlungsflüssigkeiten können zum Korrosionsschutz von Eisen und Stahl, Zink oder auch Leicht- und Buntmetallen eingesetzt werden.The treatment liquids according to the invention not only have the advantage of a high corrosion protection effect on, as can also be seen from the examples below, but also show only a minor one Foaming tendency, which has a particularly favorable effect if it is to be used by spraying. In addition, there is good resistance even in hard water. On the treated metal surfaces no crystalline drying results. The treatment fluids can be used for Corrosion protection of iron and steel, zinc or light and non-ferrous metals can be used.
Die erfindungsgemäß eingesetzten Umsetzungsprodukte können aus den Säuren und Alkanolamin bei Raumtemperatur oder erhöhter Temperatur hergestellt werden. Bei der Herstellung können auch weitere für die Behandlungsflüssigkeit erwünschte Bestandteile bereits zugemischt werden. Die erhaltenen Produkte sind klare oder auch leicht trübe flüssige Konzentrate, die auch in hartem Wasser klar löslich sind. Zur Erleichterung der Handhabung kann es zweckmäßig sein, noch Wasser zuzusetzen, um ein Konzentrat mit den vorgelösten Komponenten zu erhalten, das einen Wassergehalt von 10 bis 80% aufweistThe reaction products used according to the invention can be obtained from the acids and alkanolamine Room temperature or elevated temperature can be produced. During the production, more can also be used for the Treatment liquid desired ingredients are already mixed. The products obtained are clear or slightly cloudy liquid concentrates that are clearly soluble even in hard water. To facilitate the Handling it can be useful to add more water to a concentrate with the pre-dissolved To obtain components that have a water content of 10 to 80%
Die erfindungsgemäßen wäßrigen Behandlungsflüssigkeiten können zusätzlich noch weitere Komponenten enthalten, falls dies zweckmäßig erscheint. In vielen Fällen ist ein zusätzlicher Gehalt von Tensiden vorteilhaft, um eine gleichzeitig reinigende und entfettende Wirkung zu fördern und eine gute Benetzung der behandelten Oberflächen zu gewährleisten. Bei der Mitverwendung von Tensiden empfiehlt es sich, nichtionogene, schwach schäumende oder entschäumende Produkte, z, B. auf Basis von Anlagerungsprodukten von Äthylenoxid und/oder Propylenoxid an Alkohole, Alkylphenole, Fettsäuren, Fettamine zu wählen. Die Tenside können der Behandlungslösung in der erforderlichen Menge direkt zugesetzt werden. Zweckmäßigerweise werden sie aber bereits dem Konzentrat, das für die Herstellung der Behandlungsflüssigkeiten verwendet wird, beigegeben. Die erforderliche Menge hängt in gewissem Maße von der Wirksamkeit der jeweils verwendeten Tenside ab. Sie kann bis zu 20%, berechnet auf das wasserfreie Konzentrat, betragen.The aqueous treatment liquids according to the invention can also contain other components included if this appears appropriate. In many cases there is an additional content of surfactants beneficial to promote a cleaning and degreasing effect at the same time and good wetting of the to ensure treated surfaces. When using surfactants, it is advisable to non-ionic, weakly foaming or defoaming products, e.g. based on addition products of ethylene oxide and / or propylene oxide to alcohols, alkylphenols, fatty acids, fatty amines Select. The surfactants can be added directly to the treatment solution in the required amount. Appropriately, however, they are already added to the concentrate that is used for the production of the treatment liquids. The required The amount depends to a certain extent on the effectiveness of the surfactants used. she can be up to 20%, calculated on the anhydrous concentrate.
Wenn Leicht- oder Buntmetalle behandelt werden sollen, kann es erwünscht sein, spezielle Inhibitoren für die entsprechenden Metalle mitzuverwenden, z. B. Alkaliborate oder kondensierte Phosphate zum Schutz gegen den Angriff von Aluminium, oder Benztriazol oder dessen Derivate zum Schutz gegen den Angriff von Buntmetallen. Etwaige Zusätze solcher Inhibitoren sollen jedoch Mengen von 10%, bezogen auf das wasserfreie Konzentrat, nicht übersteigen, da sonst die Gefahr besteht, daß unerwünschte Auftrocknungen auf den Metalloberflächen auftreten.If light or non-ferrous metals are to be treated, it may be desirable to use special inhibitors for to use the corresponding metals, e.g. B. Alkali borates or condensed phosphates for protection against attack by aluminum, or benzotriazole or its derivatives for protection against attack by Non-ferrous metals. Any additions of such inhibitors should, however, amount to 10%, based on the Do not exceed anhydrous concentrate, otherwise there is a risk of undesired drying up occur on metal surfaces.
In manchen Fällen kann auch eine Mitverwendung geeigneter Bakterizide oder Fungizide angebracht sein, um die Behandlungsflüssigkeiten auch bei Raumtemperatur und nach der Aufnahme von fettigen Verunreinigungen vor Bakterien- und Pilzbefall zu schützen. AlsIn some cases it may also be appropriate to use suitable bactericides or fungicides, around the treatment fluids even at room temperature and after the absorption of greasy impurities to protect against bacterial and fungal attack. as
ίο solche Konservierungsmittel kommen in bekannter Weise z.B. Phenolderivate, Formaldehyd-abspaltende Verbindungen, Triazine, quartäre Ammoniumverbindungen in Betracht Die Zusatzmengen liegen etwa im Bereich von etwa 0,5 bis 5%, berechnet auf das wasserfreie Konzentratίο Such preservatives come in well known E.g. phenol derivatives, formaldehyde-releasing compounds, triazines, quaternary ammonium compounds into consideration The additional amounts are approximately in the range of approximately 0.5 to 5%, calculated on the anhydrous concentrate
Nachstehend sind einige Rezepturen für Konzentrate angegeben, die für die Herstellung von erfindungsgemäßen Behandlungsflüssigkeüen geeignet sind (Angaben in Gew.-%):Below are some formulations for concentrates are given for the production of the invention Treatment liquids are suitable (data in% by weight):
A)A)
UmsetzungsproduktConversion product
10 Caprylsaure10 caprylic acid
10 Gluconsäure10 gluconic acid
25 Diethanolamin25 diethanolamine
10 Nichtionogenes Tensid (C,o-irAIkohol mil 10 Mol Äthylenoxid)10 Nonionic surfactant (C, o-irAI alcohol mil 10 moles of ethylene oxide)
2,5 Bakterizid (Fnrmaldehyd-abspaltend)2.5 bactericidal (splitting off maldehyde)
5 Borax5 borax
37,5 Wasser37.5 water
C)C)
Die Konzentrate können so mit Wasser verdünnt werden, daß sich je nach Anforderung Behandlungsflüssigkeiten mit einem Gehalt an 0,5 bis 5 Gew.-% des Konzentrats ergeben. Im allgemeinen ist ein Gehalt an 1 bis 3% ausreichend.The concentrates can be diluted with water in such a way that, depending on the requirements, treatment liquids are formed with a content of 0.5 to 5 wt .-% of the concentrate. In general, a content of 1 up to 3% is sufficient.
In den nachstehenden Vergleichsversuchen wurde die Korrosionsschutzwirkung von erfindungsgemäßen Behandlungsflüssigkeiten und die von Einzelkomponenten oder anderen Zusammensetzungen geprüft. Zur Prüfung wurde das Prinzip der Arbeitsweise nachIn the following comparative tests, the anti-corrosion effect of treatment liquids according to the invention and those of individual components or other compositions tested. For testing became the principle of working according to
DIN 59 360 Blatt 2 (Entwurf Juni 1974) zur Prüfung der Korrosionsschutzeigenschaften von wasserhaltigen Kühlschmierstoffen (Späne/Filterpapier-Verfahren) angewendet Die Lösung der Proöen erfolgte jedoch jeweils in Wasser von 10° dH. Die Methode besteht im wesentlichen darin, entfettete Graugußspäne (2 g) auf einem Rundfilter mit 2 ml der jeweiligen Probelösung zu benetzen, dann die Filter 2 Stunden in einer Petri-Schale zugedeckt bei Raumtemperatur stehen zu lassen und dann das Vorhandensein von Korrosionsflecken auf dem Filterpapier auszuwerten.DIN 59 360 sheet 2 (draft June 1974) for testing the Corrosion protection properties of water-based cooling lubricants (chips / filter paper process) applied The solution of the Proöen, however, took place in each case in water of 10 ° dH. The method consists in essentially, degreased cast iron chips (2 g) on a round filter with 2 ml of the respective sample solution wet the filters in a Petri dish for 2 hours Let stand covered at room temperature and then determine the presence of corrosion stains to evaluate the filter paper.
In der nachstehenden Tabelle ist für die verschiedenen Versuche zunächst die Zusammensetzung undThe table below shows the composition and for the various experiments
Konzentration des für die Herstellung der Probelösung verwendeten Konzentrats sowie zutreffendenfalls das Mol-Verhältnis von Carbonsäure bzw. Carbonsäure-Oxicarbonsäure-Gemisch zu Alkanolamin angegeben. Der Ansatz der Probenlösungen erfolgt jeweils in 3%iger Konzentration des Konzentrates. Die erhaltenen pH-Werte sind ebenfalls angegeben. In der letzten Spalte sind die erhaltenen Bewertungsergebnisse aufgeführt Wie klar ersichtlich, wird bei Anwendung der erfindungsgemäßen Behandlungsflüssigkeiten (Versuche Nr. 7—12) eine erheblich verbesserte Korrosionsschutzwirkung erzieltConcentration of the concentrate used for the preparation of the sample solution and, if applicable, that Molar ratio of carboxylic acid or carboxylic acid-oxicarboxylic acid mixture given for alkanolamine. The sample solutions are prepared in 3% concentration of the concentrate. The pH values obtained are also given. In the last Column shows the evaluation results obtained. As can be clearly seen, when used the treatment fluids according to the invention (tests No. 7-12) have a considerably improved corrosion protection effect achieved
Claims (9)
Gluconsäure und/oder Weinsäure mit
einem oder mehreren Alkanolamine^ wobei auf 1 Mol der Säurekombination mindestens 13 Mol Alkanolamin vorliegtone or more aliphatic carboxylic acids with 6 to 10 carbon atoms and
Gluconic acid and / or tartaric acid with
one or more alkanolamines ^ with at least 13 moles of alkanolamine being present for 1 mole of the acid combination
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2614234A DE2614234C2 (en) | 1976-04-02 | 1976-04-02 | Treatment liquid for the corrosion protection of metal surfaces and concentrate for their production |
| AT150977A AT347753B (en) | 1976-04-02 | 1977-03-07 | CORROSION PROTECTION AGENT FOR METAL SURFACES |
| NL7702894A NL7702894A (en) | 1976-04-02 | 1977-03-17 | PROCESS FOR PREPARING A CORROSION PROTECTION AGENT FOR METAL SURFACES. |
| US05/781,820 US4113498A (en) | 1976-04-02 | 1977-03-28 | Corrosion inhibitor for metal surfaces |
| FR7709335A FR2346465A1 (en) | 1976-04-02 | 1977-03-29 | ANTI-CORROSION AGENT FOR METAL SURFACES |
| BE176277A BE853063A (en) | 1976-04-02 | 1977-03-30 | ANTI-CORROSION AGENT FOR METAL SURFACES |
| CA275,406A CA1084688A (en) | 1976-04-02 | 1977-03-31 | Corrosion inhibitor for metal surfaces |
| AU23863/77A AU512596B2 (en) | 1976-04-02 | 1977-04-01 | Corrosion inhibitor for metal surfaces |
| JP52036230A JPS6017829B2 (en) | 1976-04-02 | 1977-04-01 | Corrosion inhibitor for metal surfaces |
| BR7702097A BR7702097A (en) | 1976-04-02 | 1977-04-01 | WATER TREATMENT LIQUID COMPOSITION FOR ANTICORROSIVE PROTECTION OF METALLIC SURFACES AND CONCENTRATE FOR THE PRODUCTION OF A TREATMENT LIQUID |
| MX168620A MX145326A (en) | 1976-04-02 | 1977-04-01 | PROCEDURE FOR OBTAINING AN IMPROVED CORROSION INHIBITOR |
| SE7703869A SE7703869L (en) | 1976-04-02 | 1977-04-01 | CORROSION PROTECTOR FOR METAL SURFACE |
| ES457440A ES457440A1 (en) | 1976-04-02 | 1977-04-01 | Corrosion inhibitor for metal surfaces |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2614234A DE2614234C2 (en) | 1976-04-02 | 1976-04-02 | Treatment liquid for the corrosion protection of metal surfaces and concentrate for their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2614234A1 DE2614234A1 (en) | 1977-10-20 |
| DE2614234C2 true DE2614234C2 (en) | 1982-05-27 |
Family
ID=5974263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2614234A Expired DE2614234C2 (en) | 1976-04-02 | 1976-04-02 | Treatment liquid for the corrosion protection of metal surfaces and concentrate for their production |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4113498A (en) |
| JP (1) | JPS6017829B2 (en) |
| AT (1) | AT347753B (en) |
| AU (1) | AU512596B2 (en) |
| BE (1) | BE853063A (en) |
| BR (1) | BR7702097A (en) |
| CA (1) | CA1084688A (en) |
| DE (1) | DE2614234C2 (en) |
| ES (1) | ES457440A1 (en) |
| FR (1) | FR2346465A1 (en) |
| MX (1) | MX145326A (en) |
| NL (1) | NL7702894A (en) |
| SE (1) | SE7703869L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0376367A1 (en) * | 1988-12-29 | 1990-07-04 | METALLGESELLSCHAFT Aktiengesellschaft | Aqueous cleaning agent for metal surfaces |
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|---|---|---|---|---|
| US4192769A (en) * | 1978-05-12 | 1980-03-11 | The Lubrizol Corporation | Rust inhibitor additive compositions, method of making, and aqueous fluids containing the same |
| US4250042A (en) * | 1979-04-16 | 1981-02-10 | The Lubrizol Corporation | Corrosion inhibition in well-drilling operations using aqueous systems containing ammonium carboxylates |
| DE2929413A1 (en) * | 1979-07-20 | 1981-02-05 | Hoechst Ag | CORROSION PROTECTIVE AGENT FOR ALUMINUM AND ALUMINUM ALLOYS |
| US4342596A (en) * | 1980-04-10 | 1982-08-03 | Conner Alvin James Sen | Non-petroleum based metal corrosion inhibitor |
| DE3223940A1 (en) * | 1982-06-26 | 1983-12-29 | Metallgesellschaft Ag, 6000 Frankfurt | TREATMENT LIQUID FOR CORROSION PROTECTION OF METAL SURFACES AND CONCENTRATE FOR THEIR PRODUCTION |
| US4512552A (en) * | 1982-11-16 | 1985-04-23 | Katayama Chemical Works Co., Ltd. | Corrosion inhibitor |
| DE3521952A1 (en) * | 1985-06-20 | 1987-01-02 | Henkel Kgaa | AQUEOUS COMPOSITIONS FOR THE HILITE AND FLUX PROCESS AND THEIR USE |
| US5049311A (en) * | 1987-02-20 | 1991-09-17 | Witco Corporation | Alkoxylated alkyl substituted phenol sulfonates compounds and compositions, the preparation thereof and their use in various applications |
| JPS63310981A (en) * | 1987-06-12 | 1988-12-19 | Nippon Oil & Fats Co Ltd | Aqueous corrosion inhibitor |
| US5081333A (en) * | 1989-03-17 | 1992-01-14 | Mitsubishi Denki Kabushiki Kaisha | Electric discharge machining fluid with a fatty acid amide additive for rust inhibition |
| US5178786A (en) * | 1989-08-04 | 1993-01-12 | The Lubrizol Corporation | Corrosion-inhibiting compositions and functional fluids containing same |
| FR2687412B1 (en) * | 1992-02-14 | 1998-06-05 | Atochem Elf Sa | CARBOXYLIC ACID CORROSION INHIBITOR COMPOSITION AND ITS APPLICATION FOR INHIBITING CORROSION. |
| EP0556087B1 (en) * | 1992-02-14 | 1999-08-04 | Elf Atochem S.A. | Use of a composition consisting of heptanoie acid or a derivative thereof and sodium tetraborate as copper corrosion inhibitor. |
| CH686368A5 (en) * | 1993-07-19 | 1996-03-15 | Sika Ag | Additional agent for preventing the corrosion of metals in construction materials, processes for production of building materials using the corrosion inhibitor. |
| US5468412A (en) * | 1993-08-16 | 1995-11-21 | Betz Laboratories, Inc. | Low foaming aqueous cleaning and passivating treatment for metals |
| FR2736935B1 (en) * | 1995-07-21 | 1997-08-14 | Lorraine Laminage | AQUEOUS TREATMENT AGAINST CORROSION OF STEEL SHEETS COATED ON A ZINC OR ZINC ALLOY SIDE |
| US6328816B1 (en) * | 1995-07-25 | 2001-12-11 | Henkel Corporation | Composition and method for degreasing metal surfaces |
| US5747439A (en) * | 1996-04-02 | 1998-05-05 | Church & Dwight Co, Inc. | Aqueous sodium salt metal cleaner |
| US5704961A (en) * | 1996-10-17 | 1998-01-06 | Hudson; Alice P. | Corrosion inhibitors for liquid fertilizers |
| DE19654642C2 (en) * | 1996-12-28 | 2003-01-16 | Chemetall Gmbh | Process for treating metallic surfaces with an aqueous solution |
| US6124253A (en) * | 1997-09-16 | 2000-09-26 | Church & Dwight Co., Inc. | Aqueous composition for low-temperature metal-cleaning and method of use |
| US5891225A (en) * | 1998-01-23 | 1999-04-06 | Tetra Technologies Inc | Method for applying halide brines to surfaces |
| US6458320B1 (en) | 1999-04-05 | 2002-10-01 | Ashland Inc. | Galvanized metal corrosion inhibitor |
| WO2001071062A1 (en) * | 2000-03-21 | 2001-09-27 | Holland Novochem Bv | Corrosive preventive composition and method of using the same |
| US6310019B1 (en) * | 2000-07-05 | 2001-10-30 | Wako Pure Chemical Industries, Ltd. | Cleaning agent for a semi-conductor substrate |
| KR100961556B1 (en) | 2008-05-29 | 2010-06-07 | (주) 인우 코퍼레이션 | Composition of corrosion inhibitor for water soluble oil-based metal working fluid |
| US8021607B2 (en) * | 2008-10-31 | 2011-09-20 | General Electric Company | Methods for inhibiting corrosion in aqueous media |
| US8025840B2 (en) * | 2008-10-31 | 2011-09-27 | General Electric Company | Compositions and methods for inhibiting corrosion in aqueous media |
| CA2924253C (en) * | 2013-10-31 | 2018-06-19 | Amril Ag | Environmental friendly well treatment fluids comprising an ester |
| JP6444105B2 (en) * | 2014-09-17 | 2018-12-26 | 株式会社日本触媒 | Metal corrosion inhibitor for polycarboxylic acid aqueous solution, metal corrosion inhibitor aqueous solution composition, and method for inhibiting metal corrosion of polycarboxylic acid aqueous solution |
| BR112017023720B1 (en) * | 2015-05-13 | 2022-02-08 | Rhodia Operations | COMPOSITION OF CORROSION INHIBITOR AND USE THEREOF |
| KR20210104058A (en) * | 2018-12-18 | 2021-08-24 | 산 노프코 가부시키가이샤 | flash rust inhibitor |
| CN111534813B (en) * | 2020-04-29 | 2022-06-03 | 北京可林维尔化工有限公司 | Metal protective agent and preparation method and application thereof |
| CN111808457A (en) * | 2020-05-29 | 2020-10-23 | 烟台康恩环保科技有限公司 | Film forming agent and preparation method and application thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE242614C (en) * | ||||
| US2483253A (en) * | 1943-09-29 | 1949-09-27 | Swift & Co | Detergent composition |
| US2423365A (en) * | 1943-12-10 | 1947-07-01 | Petrolite Corp | Amino-ester compounds |
| US2574954A (en) * | 1947-09-23 | 1951-11-13 | Tide Water Associated Oil Comp | Rust-inhibiting compositions |
| DE867192C (en) * | 1950-07-04 | 1953-02-16 | Gerardo Collardin | Process for passivating iron and steel surfaces |
| NL89027C (en) * | 1951-06-30 | |||
| US2785989A (en) * | 1954-03-29 | 1957-03-19 | American Cyanamid Co | Metallic soaps of fatty acids and polyhydroxy monocarboxylic acids |
| US2832742A (en) * | 1954-06-09 | 1958-04-29 | Alox Corp | Corrosion inhibitor composition |
| DE1521710C3 (en) * | 1966-07-14 | 1974-07-18 | Chemische Werke Huels Ag, 4370 Marl | Use of corrosion inhibitors to protect metal surfaces that are not in contact with liquid fuels |
| FR2257703A1 (en) * | 1973-09-26 | 1975-08-08 | Volgodonskoi Khim Kombin | Corrosion-inhibiting cold-working lubricants - comprising aq. solns. of fatty acid salts |
| FR2268791A1 (en) * | 1974-04-25 | 1975-11-21 | Nobel Hoechst Chimie | Para-alkyl benzoic acid alkanolamine condensate - useful as water-soluble or dispersable corrosion inhibitors for ferrous metals |
| US4032460A (en) * | 1975-10-28 | 1977-06-28 | Union Oil Company Of California | Inhibition of scale deposition in high temperature wells |
-
1976
- 1976-04-02 DE DE2614234A patent/DE2614234C2/en not_active Expired
-
1977
- 1977-03-07 AT AT150977A patent/AT347753B/en not_active IP Right Cessation
- 1977-03-17 NL NL7702894A patent/NL7702894A/en not_active Application Discontinuation
- 1977-03-28 US US05/781,820 patent/US4113498A/en not_active Expired - Lifetime
- 1977-03-29 FR FR7709335A patent/FR2346465A1/en active Granted
- 1977-03-30 BE BE176277A patent/BE853063A/en not_active IP Right Cessation
- 1977-03-31 CA CA275,406A patent/CA1084688A/en not_active Expired
- 1977-04-01 JP JP52036230A patent/JPS6017829B2/en not_active Expired
- 1977-04-01 BR BR7702097A patent/BR7702097A/en unknown
- 1977-04-01 AU AU23863/77A patent/AU512596B2/en not_active Expired
- 1977-04-01 ES ES457440A patent/ES457440A1/en not_active Expired
- 1977-04-01 SE SE7703869A patent/SE7703869L/en unknown
- 1977-04-01 MX MX168620A patent/MX145326A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0376367A1 (en) * | 1988-12-29 | 1990-07-04 | METALLGESELLSCHAFT Aktiengesellschaft | Aqueous cleaning agent for metal surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| US4113498A (en) | 1978-09-12 |
| AT347753B (en) | 1979-01-10 |
| CA1084688A (en) | 1980-09-02 |
| MX145326A (en) | 1982-01-27 |
| AU2386377A (en) | 1978-10-05 |
| DE2614234A1 (en) | 1977-10-20 |
| NL7702894A (en) | 1977-10-04 |
| SE7703869L (en) | 1977-10-03 |
| ES457440A1 (en) | 1978-02-16 |
| JPS6017829B2 (en) | 1985-05-07 |
| JPS52129642A (en) | 1977-10-31 |
| FR2346465B1 (en) | 1981-11-27 |
| FR2346465A1 (en) | 1977-10-28 |
| BR7702097A (en) | 1978-01-10 |
| ATA150977A (en) | 1978-05-15 |
| AU512596B2 (en) | 1980-10-16 |
| BE853063A (en) | 1977-07-18 |
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| OD | Request for examination | ||
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| 8330 | Complete renunciation |